Optimizing Pore Size and Polarity in Halogen-Functionalized Metal-Organic Frameworks for Efficient Xenon/Krypton Separation: A Synergistic Strategy

ACS Appl Mater Interfaces. 2025 Jun 18;17(24):36252-36259. doi: 10.1021/acsami.5c08672. Epub 2025 Jun 6.

Abstract

High-purity xenon (Xe) is crucial in semiconductor manufacturing and medical imaging, but trace krypton (Kr) in Xe poses a significant challenge in separation due to their highly similar properties. Traditional gas separation methods are ineffective for Xe/Kr, necessitating innovative adsorbent materials. This study proposes an effective strategy using halogen-functionalized ligands to adjust the pore size and polarity in metal-organic framework (MOF) materials, achieving efficient Xe/Kr separation. A series of MOFs (LIFM-DMOF-X1, X = F, Cl, Br, I) were designed to simultaneously control pore size and wall polarity. Experimental results show that LIFM-DMOF-Cl1 and LIFM-DMOF-Br1 exhibit excellent adsorption performance and selectivity for Xe/Kr. Theoretical calculations confirm stronger Xe interactions with MOF C-H groups and halogen atoms, validating the structure-property relationship. This approach provides a synergistic strategy for developing particular gas separation materials for Xe/Kr.

Keywords: Xe/Kr separation; breakthrough; gas adsorption; halogen-functionalized; metal−organic frameworks.